Structural Basis for the Different Mechanical Behaviors of Two Chemically Analogous, Carbohydrate-Derived Thermosets

C. Maggie Lau, Sung Soo Kim, Leon M. Lillie, William B. Tolman, Theresa M. Reineke, Christopher J. Ellison

Research output: Contribution to journalArticlepeer-review

Abstract

Two renewable, structurally analogous monomers, isosorbide undecenoate (IU) and glucarodilactone undecenoate (GDLU) reacted with pentaerythritol tetrakis(3-mercaptopropionate) (PETT) via thiol-ene photopolymerization to form IU-PETT and GDLU-PETT thermosets. Despite their chemical similarity, uniaxial tensile testing showed that GDLU-PETT exhibited a strain-hardening behavior and is significantly tougher than IU-PETT. To understand this observation, in situ tensile testing and wide-angle X-ray scattering experiments (WAXS) were conducted. While the 2D WAXS patterns of IU-PETT displayed an isotropic halo during uniaxial deformation, they exhibited a change from an isotropic halo to a pair of scattering arcs for the GDLU-PETT samples. Density functional theory calculations further revealed that the GDLU alkyl chains are less angled than the IU alkyl chains. Based on these results, we postulate that the GDLU molecules can more easily order and align during uniaxial deformation, hence increasing intermolecular interactions between the GDLU molecules and contributing to the observed strain hardening behavior of their thermosets. This study exemplifies how molecules with subtle differences in their chemical structures can alter the structures and thermophysical properties of the resulting polymers in unpredictable ways.

Original languageEnglish (US)
Pages (from-to)609-615
Number of pages7
JournalACS Macro Letters
Volume10
Issue number5
DOIs
StatePublished - May 18 2021

Bibliographical note

Funding Information:
S.-S.K., C.M.L., and C.J.E. gratefully acknowledge the partial financial support from the National Science Foundation (Grant No. CBET-1659989) and by the National Science Foundation Graduate Research Fellowship Program (to C.M.L.) under Grant No. CON-75851, Project 00074041. This work was also supported in part by the National Science Foundation under the Center for Sustainable Polymers (CHE-1901635). Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from the NSF through the MRSEC (Award Number DMR-2011401) and the NNCI (Award Number ECCS-2025124) programs. The authors also thank Saumil Chheda for helpful discussions regarding the DFT calculations.

Publisher Copyright:
© 2021 American Chemical Society. All rights reserved.

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